CN111763322B - Phenyl fluorosilicone polymer and preparation method thereof - Google Patents
Phenyl fluorosilicone polymer and preparation method thereof Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 72
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 35
- 238000005336 cracking Methods 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 13
- OHABWQNEJUUFAV-UHFFFAOYSA-N dichloro-methyl-(3,3,3-trifluoropropyl)silane Chemical compound C[Si](Cl)(Cl)CCC(F)(F)F OHABWQNEJUUFAV-UHFFFAOYSA-N 0.000 claims abstract description 12
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 claims abstract description 11
- WTQAKAPKTROVFY-UHFFFAOYSA-N C[SiH]1O[Si](O[Si](O1)(CCC)F)(F)F Chemical compound C[SiH]1O[Si](O[Si](O1)(CCC)F)(F)F WTQAKAPKTROVFY-UHFFFAOYSA-N 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000047 product Substances 0.000 claims description 18
- 238000006460 hydrolysis reaction Methods 0.000 claims description 16
- 239000000413 hydrolysate Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000003292 glue Substances 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000006386 neutralization reaction Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 4
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- INAZPZCJNPPHGV-UHFFFAOYSA-N 2-[(2,4-dichloro-5-methylphenyl)sulfonyl]-1,3-dinitro-5-(trifluoromethyl)benzene Chemical compound C1=C(Cl)C(C)=CC(S(=O)(=O)C=2C(=CC(=CC=2[N+]([O-])=O)C(F)(F)F)[N+]([O-])=O)=C1Cl INAZPZCJNPPHGV-UHFFFAOYSA-N 0.000 claims description 2
- MOAZYHBAIJHHKZ-UHFFFAOYSA-N 2-ethenyl-2-methyl-1,3,5,2,4,6-trioxatrisilinane Chemical group C[Si]1(O[SiH2]O[SiH2]O1)C=C MOAZYHBAIJHHKZ-UHFFFAOYSA-N 0.000 claims description 2
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 claims 2
- -1 phenyl fluoro siloxane Chemical class 0.000 abstract description 17
- 238000009826 distribution Methods 0.000 abstract description 4
- 125000003944 tolyl group Chemical group 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 239000000499 gel Substances 0.000 description 7
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 7
- 108010009736 Protein Hydrolysates Proteins 0.000 description 5
- JJRDHFIVAPVZJN-UHFFFAOYSA-N cyclotrisiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]1 JJRDHFIVAPVZJN-UHFFFAOYSA-N 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- XGGDWTZRPQQMJC-UHFFFAOYSA-N 2,2-dimethyl-4,6-diphenyl-4,6-bis(3,3,3-trifluoropropyl)-1,3,5,2,4,6-trioxatrisilinane Chemical compound C[Si]1(O[Si](O[Si](O1)(CCC(F)(F)F)C2=CC=CC=C2)(CCC(F)(F)F)C3=CC=CC=C3)C XGGDWTZRPQQMJC-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WSNMPAVSZJSIMT-UHFFFAOYSA-N COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 Chemical compound COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 WSNMPAVSZJSIMT-UHFFFAOYSA-N 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- HAURRGANAANPSQ-UHFFFAOYSA-N cis-2,4,6-Trimethyl-2,4,6-triphenylcyclotrisiloxane Chemical compound O1[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si]1(C)C1=CC=CC=C1 HAURRGANAANPSQ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000006166 lysate Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- UNPFADACPKMIHX-UHFFFAOYSA-N 2,2-diphenyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound C1(=CC=CC=C1)[Si]1(O[SiH2]O[SiH2]O1)C1=CC=CC=C1 UNPFADACPKMIHX-UHFFFAOYSA-N 0.000 description 1
- JBSDAFPSRWMTAK-UHFFFAOYSA-N 2-prop-1-enyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound CC=C[SiH]1O[SiH2]O[SiH2]O1 JBSDAFPSRWMTAK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012676 equilibrium polymerization Methods 0.000 description 1
- BPDPTHQCDNVFLK-UHFFFAOYSA-N ethenyl(hydroxy)silane Chemical compound O[SiH2]C=C BPDPTHQCDNVFLK-UHFFFAOYSA-N 0.000 description 1
- VEJBQZZDVYDUHU-UHFFFAOYSA-N ethenyl-hydroxy-dimethylsilane Chemical compound C[Si](C)(O)C=C VEJBQZZDVYDUHU-UHFFFAOYSA-N 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/10—Equilibration processes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
Abstract
The invention relates to a phenyl fluorosilicone polymer and a preparation method thereof, which comprises the steps of firstly preparing a compound shown in a formula II by cracking trifluoropropyl methyl dichlorosilane and methyl phenyl dichlorosilane under the action of an alkaline catalyst after cohydrolysis, and then preparing the compound shown in the formula II and methyl trifluoro propyl cyclotrisiloxane (D)3F) Phenyl fluorosilicone polymer is prepared through non-equilibrium copolymerization of alkaline catalyst. Compounds of the formula II and D according to the invention3The polymerization rate of F is consistent, the even distribution of methyl phenyl siloxane chain segments in the polymer in methyl trifluoro propyl siloxane chain segments can be realized, and the phenyl fluoro siloxane polymer with high yield, good heat resistance, different viscosity or different molecular weight can be obtained without complex polymerization and post-treatment processes.
Description
Technical Field
The invention relates to a preparation method of an organic silicon polymer, in particular to a preparation method of a phenyl fluorosilicone polymer, belonging to the field of organic silicon.
Background
The fluorosilicone polymer is prepared by polymerization reaction of methyl trifluoro propyl cyclotrisiloxane, and has the characteristics of oil resistance and solvent resistance due to electronegativity and electron-withdrawing effect of fluorine atoms, so that the fluorosilicone polymer is widely applied to the oil-related sealing fields of aerospace, automobiles, machinery, chemical engineering and the like. Also, the heat resistance of the fluorosilicone polymer is lower than that of a general dimethylsiloxane polymer because the trifluoropropyl group attached to the silicon atom lowers the heat stability of the fluorosilicone polymer.
The phenyl group has oxidation resistance and thermal stability, so that the phenyl polysiloxane has better heat resistance than common polydimethylsiloxane, and the long-term use temperature can reach more than 300 ℃. In order to improve the heat resistance of fluorosilicone polymers, researchers began to consider incorporating phenyl groups into fluorosilicone polymers, such as proposed by Fiwassan et al, in "Synthesis and Properties of Fluorophenylpolysiloxane", p-trifluoromethylphenyltrifluoropropyl mixed ring body was prepared by a series of complex reactions, and then reacted with D3F equilibrium copolymerization is used for preparing phenyl-containing fluorosilicone polymer, the heat resistance of the phenyl-containing fluorosilicone polymer is obviously improved, but the method is complex in process and not suitable for industrial production; wangshuai, Zhou Zhuan in the preparation of copolymer of methyltrifluoropropylsiloxane and methylphenylsiloxane (reference 1) proposed the use of KOH as a catalyst and D3F. Methyl phenyl ring body and D3 FViThe method is used for preparing phenyl-containing fluorosilicone crude rubber by equilibrium copolymerization, and the method needs a post-treatment process of solvent washing because the ring body content in the crude rubber is too high during the equilibrium copolymerization, so that the preparation method is at the cost of sacrificing the yield, and the application requirement cannot be met; chinese patent document CN201910536793.1 (reference 2) discloses a preparation method and application of diphenyl cyclotrisiloxane, and mentions a structure of diphenyl methyl trifluoropropyl mixed cyclotrisiloxane, but due to strong electron withdrawing effect and large steric hindrance effect of diphenyl, diphenyl can be combined with D3F is copolymerized in an unbalanced state, but the reactivity ratios are still different, in the presence of D in equimolar amounts3When F is polymerized, D3The polymerization activity of F is still higher than that of the phenyl ring, and uneven distribution of phenyl in the polymer is easily caused; chinese patent document CN03128909.6 discloses a fluorine-containing mixed cyclosiloxane, a preparation method and application thereof, mentioning a preparation method of a fluorine-containing mixed ring body, but obtaining a mixture for non-equilibrium copolymerization reactionIt is not very practical to obtain phenyl fluorosilicone polymer in high yield.
At present, the problems of uniform distribution of phenyl groups on a phenyl fluorosilicone polymer molecular chain, complex preparation process, low yield, incapability of industrial production and the like can not be solved in the prior art.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a phenyl fluorosilicone polymer and a preparation method thereof, which comprises the steps of firstly preparing methyl phenyl methyl trifluoro propyl mixed cyclotrisiloxane, and mixing the methyl phenyl methyl trifluoro propyl mixed cyclotrisiloxane and D3The structure of the F is closer, the F is mutually soluble, the polymerization rate is basically consistent, and then the phenyl fluorosilicone polymer which has uniform phenyl distribution and high yield and is convenient for industrial production is prepared by non-equilibrium polymerization.
The technical scheme of the invention is as follows:
a phenyl fluorosilicone polymer having the structure shown in formula I:
in the formula I, x is greater than 0, and y is greater than 0; and the phenyl groups can be uniformly distributed on the molecular chain of the phenyl fluorosilicone polymer no matter how much the phenyl groups in the phenyl fluorosilicone polymer are.
According to the present invention, preferably, the phenyl groups in the phenyl fluorosilicone polymer are uniformly distributed, and the polymer has more excellent high and low temperature resistance.
According to the present invention, preferably, the phenyl fluorosilicone polymer is prepared from methyl trifluoro propyl cyclotrisiloxane (D)3F) And the compound of the formula II is prepared by non-equilibrium copolymerization;
according to the invention, the compound of the formula II has three spatial stereoisomers, the structure of which is shown in the formula III, and the compound of the invention can be obtained by carrying out non-equilibrium copolymerization reaction on any isomer or any combination of any isomers and methyl trifluoro propyl cyclotrisiloxane.
According to the invention, the compounds of the formula II and D3F is completely miscible with D3F, copolymerization under the condition of equimolar, the residual proportion of the two cyclic bodies in different time periods is basically kept unchanged, and the polymerization rates are basically consistent.
According to the present invention, preferably, the preparation method of the compound of formula ii comprises the following steps:
mixing trifluoropropylmethyldichlorosilane and methylphenyldichlorosilane, dropwise adding the mixture into water for hydrolysis, continuously maintaining the reaction temperature after the dropwise adding is finished, stirring to ensure that the hydrolysis reaction is complete, washing the hydrolysate to be neutral, then adding an alkaline catalyst and a cracking assistant for cracking reaction, collecting fractions at 100-110 ℃, and finally rectifying to obtain the compound of the formula II.
According to the invention, the molar ratio of the trifluoropropylmethyldichlorosilane to the methylphenyldichlorosilane is preferably 2: 1-6: 1, when the molar ratio is lower than 2:1, the chain forming property of methylphenylsiloxane chain links is too strong, the cracking is difficult, when the molar ratio is higher than 6:1, the reaction efficiency is too low, and more preferably, the molar ratio of the trifluoropropylmethyldichlorosilane to the methylphenyldichlorosilane is 3: 1-5: 1.
According to the invention, the mass ratio of the mixture of trifluoropropylmethyldichlorosilane and methylphenyldichlorosilane to water is preferably 1: 1-1: 3.
According to the invention, preferably, the reaction temperature of the hydrolysis reaction is 40-80 ℃, more preferably 60-80 ℃, the temperature is lower than 40 ℃, the hydrolysis is incomplete, a small amount of silicon-chlorine bonds exist in hydrolysate to influence the cracking reaction, and when the temperature is higher than 80 ℃, the reaction is too fast, the overflow speed of hydrogen chloride is too fast, and the operation is difficult.
According to the invention, preferably, the alkaline catalyst is NaOH, the amount of the alkaline catalyst is 1% -3% of the mass of the hydrolysate, the amount of the alkaline catalyst is less than 1%, the cracking speed is too slow, the cracking speed is not obviously improved after the amount of the alkaline catalyst is more than 3%, but the cracking yield is obviously reduced, if LiOH is used as the cracking catalyst, the cracking temperature is too high, and if KOH is used as the cracking catalyst, phenyl is easy to fall off, and crosslinking is easy to occur.
According to the invention, preferably, the cracking assistant is one or a mixture of more of benzophenone, diphenyl sulfoxide and diphenyl sulfone, and the addition amount is 10-20% of the mass of the hydrolysate.
According to the invention, preferably, the cracking temperature is 170-220 ℃, more preferably 190-210 ℃, the temperature is lower than 170 ℃, the cracking speed is too slow, even basically no cracking is carried out, the cracking temperature is higher than 220 ℃, side reactions are increased, the cracking yield is reduced, and impurities are increased.
According to the invention, preferably, the rectification temperature is 110-120 ℃, rectification is carried out under the vacuum degree of 260-270 Pa, and 105-107 ℃ fractions can be further accurately collected to obtain a compound product of the formula II.
According to the invention, the process for the preparation of the compounds of formula II, a preferred embodiment, comprises the steps of:
adding deionized water into a reactor with a mechanical stirrer, a thermometer, a condenser and a reactor, heating to 60-70 ℃, mixing trifluoropropylmethyldichlorosilane and methylphenyldichlorosilane in a molar ratio of 3: 1-5: 1, dropwise adding the mixture into water for hydrolysis, continuously maintaining the reaction temperature and stirring for 1h after dropwise adding is finished to ensure that the hydrolysis reaction is complete, washing the hydrolysate to be neutral, then adding the hydrolysate into the reactor with a pyrolysis rectifying tower, adding NaOH accounting for 1-3% of the hydrolysate and hydrolysis auxiliary agent accounting for 10-20% of the hydrolysate, controlling the vacuum degree to be 266Pa, controlling the kettle temperature to be 190-210 ℃ for pyrolysis, collecting fractions at 100-110 ℃ to obtain a lysate, rectifying the lysate at the temperature of 110-120 ℃ under the vacuum degree of 260-270 Pa, and collecting fractions at 105-107 ℃ to obtain a compound of the formula II.
According to the present invention, the preparation method of the phenyl fluorosilicone polymer comprises the following steps:
will D3And F and a compound shown in the formula II are mixed, vacuum dehydration is carried out, an alkaline catalyst, an end-capping agent and an auxiliary agent are added, heating polymerization is carried out for 1-3 h, acid glue is added for neutralization after polymerization is finished, and finally, the temperature is raised to 190 ℃ and low-boiling-point substances are removed in vacuum under the pressure of 266Pa, so that the phenyl fluorosilicone polymer is obtained.
According to the present invention, preferably, in the preparation method of the phenyl fluorosilicone polymer, D3The ratio of F to the compound of the formula II is not particularly limited, and polymerization may be carried out in any ratio as required. Preferably, D3The molar ratio of the F to the compound of the formula II is (0.1-20): 1.
according to the invention, the vacuum dehydration temperature is preferably 50-60 ℃, and the pressure is 266 Pa.
According to the present invention, preferably, the polymerization alkaline catalyst is LiOH, LiOH and D3F prepared alkali glue, NaOH and D3And F, adding 10-40 ppm of alkali glue and the like in terms of LiOH or NaOH.
According to the invention, preferably, the use of LiOH, LiOH and D3The polymerization temperature of the alkali gel catalyst prepared by F is 150-170 ℃, and NaOH, NaOH and D are used3The polymerization temperature of the alkali gel catalyst prepared by F is 110-130 ℃.
According to the present invention, preferably, the end-capping agent is a conventional end-capping agent of fluorosilicone polymer, such as vinyl fluorosilicone oil, vinyl dimethylsilanol, trimethylsilanol, etc., and the addition amount is adjusted according to the desired polymer molecular weight. The addition amount is preferably D30.01-10% of the total mass of the compounds F and II.
According to the present invention, it is preferable that the auxiliary is a vinyl auxiliary or the like, such as methylvinylcyclotrisiloxane, and the amount added is adjusted according to the desired vinyl content. The addition amount is preferably D30.001-5% of the total mass of the compounds F and II.
According to the invention, the acid colloid for neutralization is preferably composed of phosphoric acid and D3F, preparing, wherein the neutralization time is 1-3 h to neutrality. According to the inventionThe polymerization method has the yield of more than 98 percent.
The invention has not been described in detail, but is processed according to the conventional technology in the field.
The invention has the beneficial effects that:
1. compared with the traditional monomer copolymerized with fluorosilicone, the methyl phenyl methyl trifluoro propyl mixed cyclotrisiloxane of the compound of the formula II has good solubility, and the methyl phenyl methyl trifluoro propyl mixed cyclotrisiloxane has good solubility with D3F, the polymerization rate is consistent, the phenyl groups can be uniformly distributed on the molecular chain of the fluorosilicone no matter the content of the phenyl groups in the prepared polyfluorosiloxane, and the high and low temperature resistance of the rubber is improved.
2. The ring body preparation method of the invention can prepare the compound with the product purity of more than 99.0 percent, and the product purity is calculated by the sum of three kinds of spatial isomers.
3. The preparation method is simple, and the phenyl fluorosilicone polymer with high yield can be obtained without complex polymerization and post-treatment processes.
Drawings
FIG. 1 shows nuclear magnetic hydrogen spectra of the compound of formula II of example 1 of the present invention.
FIG. 2 shows the nuclear magnetic hydrogen spectrum of the polymer product of formula I of example 4 of the present invention.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following specific examples.
The raw materials used in the examples are conventional raw materials, and the equipment used is conventional equipment, commercially available products.
Example 1
Preparation of Compounds of Structure II
Adding 1000g of deionized water into a reactor with a mechanical stirrer, a thermometer, a condenser and a rectifying device, heating to a reaction temperature, mixing 633g of trifluoropropylmethyldichlorosilane and 191g of methylphenyldichlorosilane, dropwise adding the mixture into the water for hydrolysis, maintaining the reaction temperature of the system at 60-70 ℃ in the dropwise adding process, continuously maintaining the reaction temperature and stirring for 1h after the dropwise adding is finished to ensure that the hydrolysis reaction is complete, washing the hydrolysate with hot water at about 60 ℃ to be neutral, separating out a water layer to obtain 654g of hydrolysate, adding the hydrolysate into the reactor with a cracking rectifying tower, adding 13g of NaOH (diluted into 50% aqueous solution) and 90g of benzophenone, gradually heating to about 100 ℃, dehydrating under the pressure of 10.1kPa, gradually heating to about 185 ℃, reducing the pressure to about 266Pa, controlling the temperature of the reactor for cracking, collecting fractions at 100-110 ℃, transferring the fractions to the rectifying device, the rectification temperature is 110-120 ℃, the pressure is 266Pa, 105-107 ℃ fractions are collected to obtain a compound product of the formula II, the product purity is 99.2%, and the yield is 78%.
Compounds of the formula II and D3The experimental process of the F equal molar ratio reactivity ratio is as follows in the following table 1: 44.8g of the above-mentioned compound of the formula II after drying and dried D are charged into the polymerization reactor3And F46.8g, replacing with nitrogen, heating to 110 ℃, adding 0.05g of NaOH alkali gel to maintain the reaction temperature at 110-120 ℃, sampling every 10 minutes, neutralizing with acetic acid, and performing gas chromatography analysis to determine the residual content of the two monomers until the material is gelatinous.
TABLE 1 Compounds of formula II and D3F reactivity ratio experimental table
Table 1 shows that, throughout the copolymerization, the two ring bodies are polymerized in equal proportions, i.e.the compound of the formula II with D3There is little difference in the open loop rate of F.
The nuclear magnetic hydrogen spectrum of the compound product of the formula II is shown in figure 1, wherein a methyl hydrogen signal connected with a trifluoropropyl group on the same silicon atom is shown at 0.27ppm, a methyl hydrogen signal connected with a phenyl group on the same silicon atom is shown at 0.41ppm-0.48ppm, a methylene hydrogen signal connected with silicon on the trifluoropropyl group at 0.90ppm, a middle methylene hydrogen signal on the trifluoropropyl group at 2.09ppm, and a hydrogen signal on the phenyl group connected with silicon is shown at 7.38ppm-7.57 ppm.
Example 2
Preparation of Compounds of Structure II
Adding 1500g of deionized water into a reactor with a mechanical stirrer, a thermometer, a condenser and a condenser, heating to a reaction temperature, mixing 844g of trifluoropropylmethyldichlorosilane and 191g of methylphenyldichlorosilane, dropwise adding the mixture into the water for hydrolysis, maintaining the temperature of the system at 70-80 ℃ in the dropwise adding process, continuously maintaining the reaction temperature and stirring for 1h after the dropwise adding is finished to ensure that the hydrolysis reaction is complete, washing the hydrolysate to be neutral by using hot water at about 60 ℃, separating out a water layer to obtain 802g of hydrolysate, adding the hydrolysate into the reactor with a cracking and rectifying tower, adding 10g of NaOH (diluted into 50% of water solution) and 100g of diphenyl sulfoxide, gradually heating to about 100 ℃, dehydrating under the pressure of 10.1kPa, gradually heating to about 185 ℃, reducing the pressure to about 266Pa, controlling the temperature of the reactor for cracking, collecting 100-110 ℃ fractions, transferring the fractions to a distillation device, the rectification temperature is 110-120 ℃, the pressure is 266Pa, 105-107 ℃ fractions are collected to obtain a compound product of the formula II, the product purity is 99.4%, and the yield is 81%.
Example 3
Preparation of Compounds of Structure II
Adding 1000g of deionized water into a reactor with a mechanical stirrer, a thermometer, a condenser and a rectifying device, heating to a reaction temperature, mixing 422g of trifluoropropylmethyldichlorosilane and 191-methylphenyldichlorosilane, dropwise adding the mixture into the water for hydrolysis, maintaining the temperature of the system at 70-80 ℃ in the dropwise adding process, continuously maintaining the reaction temperature and stirring for 1h after the dropwise adding is finished to ensure that the hydrolysis reaction is complete, washing the hydrolysate to be neutral by using hot water at about 60 ℃, separating out a water layer to obtain 493g of hydrolysate, adding the hydrolysate into the reactor with a cracking rectifying tower, adding 7.4g of NaOH (diluted into 50% of water solution) and 70g of diphenyl sulfoxide, gradually heating to about 100 ℃, dehydrating under the pressure of 10.1kPa, gradually heating to about 190 ℃, reducing the pressure to about 266Pa, controlling the temperature of the reactor for cracking, collecting fractions at 100-110 ℃, transferring the fractions to the rectifying device, the rectification temperature is 110-120 ℃, the pressure is 266Pa, 105-107 ℃ fractions are collected to obtain a compound product of the formula II, the product purity is 99.1%, and the yield is 72%.
Example 4
Preparation of Fluorosiloxane Polymer having phenyl content of 5%
398gD was added to the polymerization reactor3F and 67.2g of a compound shown in the formula II are dehydrated for 2h in vacuum at 50-60 ℃ and under the pressure of 266Pa, 0.3g of LiOH alkali gel catalyst (the content of LiOH is 3.31 percent) and 23.8 percent trimethylsilanol are added, the temperature is raised to 150-160 ℃ for polymerization for 3h, 0.6g of phosphoric acid gel (the content of phosphoric acid is 4.02 percent) is added for neutralization after the polymerization is finished, finally the temperature is raised to 190 ℃, the pressure is reduced to 266Pa, and low-boiling-point substances are removed for 2h in vacuum to obtain the phenyl fluorosilicone polymer. The product is colorless transparent liquid at-50 deg.c, viscosity is 780cp, volatile component is 2.2% and yield is 98.2%.
The nuclear magnetic hydrogen spectrum of the polymer product is shown in figure 2, wherein a methyl hydrogen signal connected with a trifluoropropyl group on the same silicon atom is shown at 0.26ppm, a lower signal near 0.26ppm is a methyl hydrogen signal connected with a phenyl group on the same silicon atom, a methylene hydrogen signal connected with silicon on the trifluoropropyl group is shown at 0.85ppm, a middle methylene hydrogen signal on the trifluoropropyl group is shown at 2.08ppm, a hydrogen signal on the phenyl group connected with silicon is shown at 7.15ppm-7.68ppm, and a hydrogen signal on solvent deuterated chloroform is shown at 7.25 ppm.
Example 5
Preparation of Fluorosiloxane Polymer having a phenyl content of 15%
Adding 257gD into the polymerization kettle3F and 202g of a compound shown in the formula II are dehydrated for 2h in vacuum at 50-60 ℃ and under the pressure of 266Pa, 0.25g of NaOH alkali gel catalyst (the content of NaOH is 3.98%) and 9.8g of vinyl silanol are added, the temperature is raised to 120-130 ℃ for polymerization for 2h, 0.38g of phosphoric acid gel (the content of phosphoric acid is 4.02%) is added for neutralization after the polymerization is finished, finally the temperature is raised to 190 ℃, the pressure is reduced to 266Pa, and low-boiling-point substances are removed for 2h in vacuum to obtain the phenyl fluorosilicone polymer. The product is colorless transparent liquid at-50 deg.c, viscosity of 5200cp, volatile 1.8% and yield of 98.5%.
Example 6
Preparing fluorosilicone raw rubber with 8 percent of phenyl content
356gD was added to the polymerization kettle3F and 106.5g of a compound shown in the formula II, dehydrating the mixture for 2 hours in vacuum at the temperature of between 50 and 60 ℃ and under the pressure of 266Pa, and adding 0.18g of NaOHHeating an alkali glue catalyst (the NaOH content is 3.98 percent), 1.26g of methyl vinyl cyclotrisiloxane and 0.2g of trimethylsilanol to 120-130 ℃ for polymerization for 2 hours, adding 0.27g of phosphoric acid glue (the phosphoric acid content is 4.02 percent) for neutralization after the polymerization is finished, finally heating to 190 ℃, reducing the pressure to 266Pa, and removing low-boiling-point substances in vacuum for 2 hours to obtain the phenyl fluorosilicone polymer. The product is colorless transparent jelly, the molecular weight is 103 ten thousand, the volatile component is 0.9 percent, and the yield is 98.9 percent.
Comparative example 1
Preparation of Fluorosiloxane Polymer having phenyl content of 5%
The specific implementation steps are the same as those in the embodiment 4, and the differences are as follows: instead of 67.2g of the compound of the formula II, 20.4g of trimethyltriphenylcyclotrisiloxane were used, and the final polymer was cloudy.
Trimethyl triphenyl cyclotrisiloxane is used as raw material and D3The turbidity of the final product of the F copolymerization is caused by incompatibility of the two products and too large difference of polymerization rates, so that synchronous reaction cannot be carried out during polymerization, and the chain links of the methyl phenyl siloxane are not uniformly distributed.
Comparative example 2
Preparation of Fluorosiloxane Polymer having phenyl content of 5%
The specific implementation steps are the same as those in the embodiment 4, and the differences are as follows: using 35.7g of diphenylbis (trifluoropropyl) dimethylcyclotrisiloxane (patent CN201910536793.1) instead of 67.2g of the compound of formula II, a transparent liquid was finally obtained as a polymer, which was a hazy, translucent liquid at-50 ℃.
Diphenyl bis (trifluoropropyl) dimethylcyclotrisiloxane is used as raw material and D3The final product of the F copolymerization is transparent, but the hazy and translucent at low temperature is due to the fact that diphenyl bis (trifluoropropyl) dimethylcyclotrisiloxane and D are reacted3F has good compatibility and can react at the polymerization temperature, but the polymerization rate of the diphenyl bis (trifluoropropyl) dimethylcyclotrisiloxane is lower than that of D due to the steric hindrance of diphenyl3F, in the early stage of the polymerization, is replaced by D3F polymerization is dominant, and D is the later stage3The copolymerization of the two occurs only after the concentration of F is reduced, i.e. the phenyl groups are dispersed and not uniform in the polymer, the table is maintained at a high temperatureIt is not obvious that when the temperature is reduced, the phenyl group content in the polymer is high, and the polymer is separated out at one section and becomes semitransparent.
Test example 1
The fluorosilicone polymer with 5% phenyl content in example 4, the fluorosilicone polymer with 15% phenyl content in example 5, and the fluorosilicone green stock with 8% phenyl content in example 6 were prepared by the methods of document 1 and document 2, respectively, and had high and low temperature resistance as shown in table 2 below.
TABLE 2 comparison table of high and low temperature data of phenyl polyfluorosiloxane by different methods
Note: document 1: wangshuai, Zhoujik, preparation of copolymer of methyltrifluoropropylsiloxane and methylphenylsiloxane, 2016, university of Shandong; document 2: chinese patent document CN 201910536793.1.
Table 2 above shows that, three phenyl fluorosilicone polymers corresponding to examples 4, 5, and 6 have more uniform phenyl distribution, and thus have improved high and low temperature resistance compared to the same polymer prepared by the method of document 1, improved high temperature resistance compared to the same polymer prepared by the method of document 2, and significantly improved low temperature resistance.
Claims (16)
1. A phenyl fluorosilicone polymer, wherein the polymer has a structure shown in formula I:
the compound has a structure shown in a formula I,
in the formula I, x is greater than 0, and y is greater than 0; and the phenyl groups can be uniformly distributed on the molecular chain of the phenyl fluorosilicone polymer no matter how much the phenyl groups in the phenyl fluorosilicone polymer are.
2. The method of claim 1The phenyl fluorosilicone polymer is characterized in that the phenyl fluorosilicone polymer is prepared from methyl trifluoro propyl cyclotrisiloxane (D)3F) And the compound of the formula II is prepared by non-equilibrium copolymerization;
and (5) formula II.
3. The phenylfluorosilicone polymer according to claim 2, wherein the preparation method of the compound of formula ii comprises the steps of:
mixing trifluoropropylmethyldichlorosilane and methylphenyldichlorosilane, dropwise adding the mixture into water for hydrolysis, continuously maintaining the reaction temperature after the dropwise adding is finished, stirring to ensure that the hydrolysis reaction is complete, washing the hydrolysate to be neutral, then adding an alkaline catalyst and a cracking assistant for cracking reaction, collecting fractions at 100-110 ℃, and finally rectifying to obtain the compound of the formula II.
4. The phenylfluorosilicone polymer according to claim 3, wherein the molar ratio of trifluoropropylmethyldichlorosilane to methylphenyldichlorosilane is 2:1 to 6: 1.
5. The phenylfluorosilicone polymer according to claim 3, wherein the mass ratio of the mixture of trifluoropropylmethyldichlorosilane and methylphenyldichlorosilane to water is 1:1 to 1: 3.
6. The phenyl fluorosilicone polymer of claim 3, wherein the reaction temperature of the hydrolysis reaction is 40 ℃ to 80 ℃.
7. The phenyl fluorosilicone polymer of claim 3, wherein the alkaline catalyst is NaOH, and the amount of the alkaline catalyst is 1% to 3% of the mass of the hydrolysate.
8. The phenylfluorosilicone polymer according to claim 3, wherein the cracking assistant is one or more of benzophenone, diphenyl sulfoxide and diphenyl sulfone, and the addition amount is 10-20% of the mass of the hydrolysate.
9. The phenylfluorosilicone polymer of claim 3, wherein the cracking temperature is from 170 ℃ to 220 ℃.
10. The phenyl fluorosilicone polymer of claim 3, wherein the rectification temperature is 110-120 ℃, and the rectification is carried out under the pressure of 260-270 Pa to obtain the compound product of formula II.
11. The method for preparing phenyl fluorosilicone polymer according to claim 2, comprising the steps of:
will D3And F and a compound shown in the formula II are mixed, vacuum dehydration is carried out, an alkaline catalyst, an end-capping agent and an auxiliary agent are added, heating polymerization is carried out for 1-3 h, acid glue is added for neutralization after polymerization is finished, and finally, the temperature is raised to 190 ℃ and low-boiling-point substances are removed in vacuum under the pressure of 266Pa, so that the phenyl fluorosilicone polymer is obtained.
12. The method for preparing phenyl fluorosilicone polymer according to claim 11, wherein the vacuum dehydration temperature is 50 to 60 ℃ and the pressure is 266 Pa.
13. The method for preparing phenylfluorosilicone polymer according to claim 11, wherein the polymerization reaction basic catalyst is LiOH, LiOH and D3F prepared alkali glue, NaOH and D3And F, adding 10-40 ppm of alkali glue calculated by LiOH or NaOH.
14. The method of claim 13, wherein LiOH, LiOH and D are used3F preparation ofThe polymerization reaction temperature of the alkali gel catalyst is 150-170 ℃, and NaOH, NaOH and D are used3The polymerization reaction temperature of the alkali gel catalyst prepared by the F is 110-130 ℃.
15. The method for preparing phenyl fluorosilicone polymer according to claim 11, wherein the end capping agent is vinyl fluorosilicone oil, vinyl dimethylsilicone or trimethylsilicone, and the addition amount is D30.01-10% of the total mass of the compound F and the compound II.
16. The method for preparing phenyl fluorosilicone polymer according to claim 11, wherein the auxiliary agent is methyl vinyl cyclotrisiloxane added in an amount of D30.001-5% of the total mass of the compound F and the compound II.
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| US4075170A (en) * | 1976-08-12 | 1978-02-21 | Alexei Ivanovich Ponomarev | Fluorosiloxane rubbers and process for producing same |
| US4585848A (en) * | 1981-04-09 | 1986-04-29 | Evans Edwin R | Fluorosilicone rubber composition, process and polymer |
| CN104448319A (en) * | 2014-11-17 | 2015-03-25 | 华东理工大学 | Method for preparing organic silicon copolymer |
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